Recovery of methyl ethyl ketone from azeotropic distillates by extraction with tetraethylene glycol



July 6, 1948. s. R. LAKE RECOVERY OF METHYL ETHYL KETONE FROM AZEOTROPIC DISTILLATES BY EXTRACTION WITH TETRA-ETHYLENE GLYCOL Filed Oct. 18. 1941 Patented July 6, 1948 n RECOVERY OF METHYL ETHYL KETONE FROM AZEOTROPIC'DISTILLATES BY EX- TRACTION WITH TETRAETHYLENE GLY- COL George R. Lake, LongBeach, Calif., assigner to Union Oil Company of California, Los Angeles, Calif., a corporation of California Application October 18, 1941, Serial No. 415,567

2 Claims. (Cl. 2412-42) This invention relates to a process of azeotropic distillation to prepare pure hydrocarbons from complex petroleum fractions which are dilcult to separate by ordinary fractional distillation due to the small diierences in boiling points of the hydrocarbons contained in the petroleum fraction. The invention is particularly directed to an improved process for separating the hydrocarbons and the azeotrope former that are con tained in the azeotropic distillate produced by the azeotropic distillation.

The process of separating one hydrocarbon component from another hydrocarbon component of substantially the same boiling point contained `in a complex hydrocarbon fraction by azeotropic the'reiatively more parainic hydrocarbons together with the extraneous substance leaving as undistilled bottoms the relatively less paraillnic hydrocarbons which may or may not contain a portion of the extraneous substance. present description of my invention the aforesaid type of fractional distillation will be referred to as azeotropic distillation, the extraneous substance or substances which are added to the complex hydrocarbon fraction to eiect the aforementioned change will be referred to as azeotrope formers and the overhead from the azeotropic distillation will be referred to as the azeotropi'c distillate.

One of the main dliiculties in the azeotropic distillation process is in the separation or recovery of the azeotrope former from the hydrocarbons contained in the azeotropic distillate. One of the methods proposed for this purpose resides in washing the azeotropic distillate with water which is adapted to dissolve the azeotrope former from the azeotropic distillate and thus be separated from the hydrocarbons by settling and stratification. The solution of azeotrope former and Water may be distilled to separate the azeotrope former from the water.

However, diiiiculty has been experienced to separate the azeotrope former substantially com- In the- 2 pletely from the azeotropic distillate by washing with water since in many cases, the azeotrope former has a preferential solubility in the hydrocarbons as compared with the solubility in the water. The result is that the hydrocarbons must be Washed with an excessively large amount of water in order to remove the last traces of the azeotrope former so that the hydrocarbons may be utilized and the azeotrope former recovered without sustaining a substantial loss of this more valuable material. To illustrate, it has been found that methyl ethyl ketone, particularly containing about 10% by volume of water, is a very eicient azeotrope former to eiect the separationof non-aromatic hydrocarbons from a hydrocarbon fraction containing toluene. Yet the use of this azeotrope former oiers the serious diiilculty of recovering the methyl ethyl ketone from the azeotropic distillate. While the separation of the methyl-ethyl ketone may be accomplished by washing with water, this h'as required about five or six volumes of water for each `volume of azeotropic distillate. Even by washing the azeotropic distillate with this large amount of water. the hydrocarbons thus separated still contained about one percent of methyl ethyl ketone. ther-more, in order to recover the methyl eth'yl ketone from the very dilute Wash solution, it is dilute methyl ethyl ketone.

It is thus an object of my invention to eiect a substantially complete separation of the azeotrope former from the hydrocarbons contained in the azeotropic distillate and it is a particular object to eiiect the aforesaid separation in an eiilcient and economical manner without loss of azeotrope former.

It is a further object of my invention to effect the separation of the azeotrope former from the azeotropic distillate by the use of selective solvents having a preferential solubility for the azeotrope former than for the hydrocarbons contained in the azeotropic distillate. A further object is to eiect the separation with the use of a smaller amount of the selective solvent than required when using Water for this purpose.

I have discovered that a substantially complete separation of the azeotrope former from the azeotropic distillate may be accomplished by the use of selective solvents having a preferential solubility for the azeotrope former than for the hydrocarbons. invention may be accomplished by simply intimately contacting or mixing the azeotropic distillate with a sufficient amount of selective solvent Fure Thus, theseparation according to my at a, suitable temperature to enable the selective solvent to dissolve or extract the azeotrope former, allowing th'e mixture to settle and stratify into two layers, generally, an upper layer of y the hydrocarbons and a lower layer of the azeotrope former dissolved in the selective solvent and withdrawing one layer from the other layer.

To illustrate thel advantage of employing a selective solvent for effecting the separation of the azeotrope former from the azeotropic distillate, an azeotropic distillate ofihydrocarbons and methyl ethyl ketone of identical composition as that described above which was' washed with water, was extracted with tetra ethylene glycol employing only about three volumes of the solvent to one of the azeotropic distillate. The hydrocarbons thus recovered were substantially free from methyl ethyl ketone. Thus, it is possible by my invention to produce a hydrocarbon fraction which' is free of azeotrope former by employing aconsiderably less amount of the solvent than when the azeotropic distillate is extracted with Water.

Besides tetra ethylene glycol mentioned above, selective solvents which I have found suitable to effect the extraction of azeotrope formers from azeotropic distillates include phenolic compounds such as resorcinol, para-chlorophenol, phenol, yxylenol, pyrogallol, pyrocatechol and cresylic acid, polyhydric alcohols such as di, tri, tetraand hexaethylene glycols and dipropylene glycol, amines such as mono, di, andtri-ethanolamine, 2-methyl propanol amine, diethylene triamine, triethylene tetramine, tetra-ethylene pentamine, diethylene diamine, tri-ethylene triamine, di-

phenylamine, xylidine, aniline, ortho phenylene diamine, alpha naphthol amine and phenyl hydrazine, fatty acids s uch as acetic, propionic and formic acids, aliphatic alcohols such as methyl, ethyl, isopropyl, tertiary butyl and normal propyl alcohols, ketones such as methyl ethyl ketone and acetone, `cyclic ketones such as cyclohexanone, yalhrl ethers of polyglycols such as mono ethyl ether of diethylene glycol and ethyl ether of ethylene glycol, heterocyclic compounds such as furfuryl alcohols, tetrahydro furfuryl alcohol, dioxane,'morpholine, piperidine and thiophene, nitroparains such as nitromethane, nitroethane and nitropropane.

In addition to the above, aromatic hydrocarbon solvents may be employed to effect the desired separation -since the azeotrope farmers have a greater lafilinity for these hydrocarbons than they have for the relatively non-aromatic hydrocarbons contained in the azeotropic distillate. Aromatic hydrocarbon solvents useful for the purpose include benzene, toluene,` xylenes, etc.

Of the above selective solvents; I have found the polyhydric alcohols such as di, triand tetra ethylene glycols, amines such as monoand triethanolamine and diethylene triamine, and alsc resorcinol andnitromethane to be particularly eilicient for extracting such azeotrope formers as methyl ethyl ketone and methanol from azeotropic distillates containing non-aromatic hydrocarbons having a boiling range of 200 to 240 F.

Azeotrope formers which may be separated according to my invention from azeotropic distillates produced by azeotropic distillation include all of the compounds disclosed above as selective solvents for separating the azeotrope former from the azeotropic distillate. However, in effecting a separation of the azeotrope former from an' azeotropic distillate, it is obvious that the same material should not be employed as a selective solvent as was employed to effect the azeotropic distillation. Whether a particular material will function as a selective solvent to separate the azeotrope former from the azeotropic distillate depends upon the character of the azeotropic distillate such as the boiling point and solu bility characteristics of the hydrocarbons and oi the azeotrope former contained therein. For example, a compound may be eillclent to perform the azeotropic distillation to separate hydrocarbons from a particular complex hydrocarbon fraction and may be inefficient to separate hydrocarbons from a complex hydrocarbon fraction of a different boiling point; yet this same compound may be useful as a selective solvent to separate a different azeotrope former from the azeotropic distillate produced from such complex hydrocarbon fraction of diierent boiling point. To illustrate specifically, tetra ethylene glycol is a particularly eilicient azeotrope former for separating relatively paraiiinic hydrocarbons in the lubricating oil boiling range from the relatively nonparailinic oil fractions and is of less efficiency for separating non-aromatic hydrocarbons from a toluene fraction. However, the tetra ethylene glycol is an eillcient selective solvent for removing an emcient azeotrope former such as methyl ethyl ketone from the azeotropic distillate obtained from the azeotropic distillation of a toluene fraction.

In selecting a selective solvent for the separation of azeotrope former from a particular azeotropic distillate, it is preferable to choose one which has a materially different boiling point, either higher or lower, than that of the azeotrope former so that the separation of the azeotrope former and selective solvent from each other may be readily accomplished by simple fractional distillation.

Other objects, features and advantages of my invention will be apparent to those skilled in the art from the following description of the invention which represents a diagrammatic arrangement of apparatus for carrying out my invention. In the following example, the invention will be described as applied to the separation of toluene from a hydrocarbon fraction employing methyl ethyl ketone containing about 10% by volume of water. However, it will be observed that this ex- Vample is not to be taken as limiting my invention since the process is applicable to separate other components from complex substances employing other azeotrope formers under conditions adapted to effect the desired separation.

In the drawing, the hydrocarbon feed to be resolved into its component parts, preferably one having a narrow boiling range, not more than 50 F., such as for example, a hydrocarbon fraction having a boiling range of about 200 to 240 F. and consisting of substantially 45% by volume of toluene, 6% by volume of oleflns and the remainder, parailln and naphthene hydrocarbons, obtained by fractionation of a catalytically reformed gasoline is taken from tank I0 via line H vand is pumped by pump I2 through line Il controlled by valve I5 into line I6. Azeotropeformer, such as methyl ethyl ketone, containing about 10% water, is taken from tank l1 via line i8 controlled byV valve Il and is pumped by pump 20 through lines 2| and 22 and valve 23 into line I8 where it is mixed with the hydrocarbon feed from tank I0. The mixture of hydrocarbon feed and azeotrope former infthe. ratio of approximately two parts of the azeotrope former and Que part of hydrocarbon feed in the example herein given, is passed into fractionating column it where the mixture is subjected to fractionation, heat being supplied by closed steam coil 25. If desired, the azeotrope former may be introduced directly into the fractionating column at any other point as near the top of the column in which case it will act in part as reux for the fractionation or reflux may be obtained by cooling coil 25a., In the fractionating column, the distillation is controlled so as to distill overhead an azeotrope consisting of the parafiln, olefin and naphthene hydrocarbons together with substantially all of the methyl ethyl ketone and water. In the example herein given, this is accomplished at an overhead temperature of approximately 1GO-170 F. and at atmospheric pressure. If4 desired, the azeotropic distillation may be carried out either at atmospheric or super atmospheric pressure or under a vacuum.

The type of distillation to be used depends somewhat on the quantity of the azeotrope former used. I may distill over any proportion of the petroleum fraction to be subjected to azeotropic distillation that I desire by adjusting the quantity of azeotrope former. Thus, by employing a relatively small proportion of the azeotrope former, it is possible to distill overhead a portion of the relatively non-aromatic hydrocarbons and leave a portion as bottoms with the relatively aromatic hydrocarbons, or by employing a relatively larger amount of the azeotrope former, it is possible to distill all of the relatively non-aromatic hydrocarbons and a portion of the relatively aromatic hydrocarbons, leaving relatively aromatic hydrocarbons as still bottoms.

The overhead mixture is removed from the fractionating column via line 26, controlled by valve 21, condensed in condenser 28'and passed via line ZQ-into line 30 controlled by valve 30a to the methyl ethyl ketone-water recovery system, as will be described hereinafter. In some cases, depending upon the hydrocarbon feedand the character and composition of the azeotrope former, the azeotropic distillate obtained in line 26 will separate into two phases when properly cooled. In the case of the example herein described, cooling of the azeotropic distillate to about 5070 F., the condensate will separate when allowed to settle into an upper phase comprising the bulk of the azeotropic distillate and consisting of substantially all of the hydrocar-A bons and most of the methyl ethyl ketone and a lower phase consisting of substantially al1 of the water containing the remainder of the methyl ethyl ketone. In such case, it is preferable to pass the cooled azeotropic condensate from condenser 2d through lines 29 and 3i controlled by valve @la into a separator 32 where the mixture is allowed to stratify into the two layers. The lower layer is withdrawn via line 3d and passed by pump 32a via line 33 controlled by valve 33a to a recovery system for the recovery of the methyl ethyl ketone, as will be described hereinafter. The upper layer is withdrawn via line 3E and passed via line 3@ to the methyl ethyl ketone recovery system.

Certain azeotrope formers such as ltetra ethylene glycol employed for the separation of high boiling parafinic hydrocarbons such as lubricating oil fractions will substantially completely separate into an upper phase of hydrocarbons containing very small, if any, azeotrope former and a. lower layer of azeotrope former containing very little, if any, hydrocarbons. In such cases, it may be desired to effect a separation of the two phases in separator 32 and recycle the lower phase to the azeotropic distillation in 2t as by line M, pump 32a and lines 22 and it. In some cases, the azeotropicdistillatlon as noted above, may be carried out to distill overhead all of the relatively parafflnic hydrocarbons together with a portion of the relatively non-paramnic hydrocarbons, particularly the lower boiling nonparamnic hydrocarbons. In this case, the cooling oi the azeotropic distillate may be controlled to separate it into two phases consisting of an upper phase of the relatively parafinic hydrocarbons and a lower layer of the relatively nonparamnlc hydrocarbons dissolved in the azeotrope former. The latter may be separated from the upper phase and the relatively non-paraiiinic hydrocarbons recovered therefrom.

The bottoms in the fractionating column 2d I consisting of the aromatic fraction or toluene azeotrope former, the bottoms from the fraction' ating column may be passed directly via lines 36, 39, d@ controlled by valve di, d2, d3 controlled by valve dit and d5 into storage tank t6. However, in the event the charging stock has not been carefully fractionated to remove aromatic hydrocarbons heavier than toluene, such as xylene,

etc., the bottoms-in the fractionating column 2d i will contain all or substantial amounts of such aromatic hydrocarbons. In the event it is desired to recover the aromatic hydrocarbon mixture per se, it is passed directly to tank 46 as described above. However, if it is desired to separate the toluene from the remaining aromatic hy drocarbons, the bottoms are passed via lines 36, 39, t0, d2 into line il controlled by valve d8 from which it passes throughl heater 49 and line 50 into fractionating column 5i where the mixture is fractionated to remove the toluene as an overhead product aided by heat from the heater 52. The vaporized toluene is removed from the top' of the fractionating column 5I via line B3, con-I densed in condenser 5d and passed via line 55 into collecting tank 56. The condensate may be withdrawn from the collecting tank by pump 51 and passed into line 58. If desired, part of the condensate may be cycled via line 59 controlled by valve t@ to the fractionating column 5| to serve as reflux for the fractionation. The remaining portion is passed via line Gi controlled by valve G2 through line H5 into storage tank Mi. The Ibottoms from the fractionating column, consisting of xylene or a mixture of xylene and higher boiling aromatic hydrocarbons, is withdrawn via line 63 controlled by valve et and pumped by pump G5 and line 6G into storage tank 61.

In the event the'bottoms fraction from the fractionating column 2d contains a portion of the azeotrope former, this may be removed by passing the bottom fraction via lines 36, 39 and .68 controlled by valve 69 through heater 'l0 and line 1i into fractionating column "i2 provided with a heater 13 and reflux cooling coil 1t where the azeotrope former may be fractionated and removed via line 15, condensed in condenser 16 and passed via line 11 into collecting tank 1B from which lt may be returned to the fractionating column 24 by pump 1B and line 80 controlled by valve 8| and lines 22 and i5. The bottoms from the fractionating column 12 may be passed via line l2 controlled -by valve 83 into line' 42 from which it may be passed by pump Neither directly to the storage tank 45 or to fractionating column in accordance with the above disclosure.

The toluene or the mixture of toluene and higher boiling aromatic hydrocarbons obtained in tank 45 and the higherboiling aromatic hydrocarbons obtained in tank 51 may be treated with clay which may be accomplished at a temperature of about 230 F. employing 1 to 5 pounds of clay per barrel of the hydrocarbon fraction. If

r desired, the clay treatment may precede the fractionation in fractionating column 5| in which case the fractionation in 5| may serve either to rerun the clay treated stock and/or to fractionate the high boiling aromatic hydrocarbonsy from the toluene. In place of clay treatment, the aromatic fraction may be cooled and then treated with l to pounds of sulfuric acid per Ibarrel of the hydrocarbons followed by neutralization with clay or caustic alkali. The acid treatment serves to remove small traces of undesirable unsaturated hydrocarbons which may be detrimental in color stability and nitration of the toluene.

In order to recover the azeotrope former from the azeotropic distillate either as a total fraction as that passing through valve a or as a portion thereof as passing through line 35, the mixture is passed via line 85 into extractor 86 which is provided with packing material, such as broken tile 81 where it is countercurrently contacted with a selective solvent adapted to extract the methyl ethyl ketone and water from the mixture.

The selective solvent is obtained from tank 88 and passed via line 89 controlled by valve 90 and pumped by pump 9| into the extractor 85. As selective solvents adapted for the purpose, tetra ethylene glycol is particularly suitable when used in about two volumes to one of the azeotropic distillate at about atmospheric temperature.

The non-aromatic hydrocarbons, if relatively free of azeotrope formers, are withdrawn from the top of the extractor 86 via line 92 and are passed through valve 83 and line 34 and are pumped by pump 95 through line 88 into storage tank 31. If these hydrocarbons contain selective solvent, they may be subjected to fractionation for the recovery of the selective solvent. In the event the .non-aromatic hydrocarbons contain azeotrope formers and suspended selective solvent, it is preferable to pass the mixture via valve 38 into a separator 98 when the suspended selective solvent settles and is withdrawn via valve |50 and pumped by pump 0| into line |02. The hydrocarbons containing an azeotrope former in solution is passed via line |03 through heater |04 into fractionating column |05 provided with heating coil |05 and reflux cooling coil |01 where they are subjected to fractionation to remove remaining traces of the methyl ethyl ketone and -water and also a portion of the non-aromatic hydrocarbons. These pass via line |05, condensed in condenser |09 and collected in collecting tank III from which the condensate may be passed via line III controlled by valve ||2 and pumped by pump H4 through lines ||5 and 85 into extractor 05 where the mixture is re-extracted. The bottoms from the fractionating column, |05 consisting of non-aromatic hydrocarbons are withdrawn via line H0 and passed viaI line 90 controlled by valve and pumped by pump 95 into storage heater |26 where the mixture is fractionated to separate the azeotrope former which may con- 'sist of the methyl ethyl ketone containing about 10% by volume of water as an overhead vapor which may be passed via line |21 controlled by valve |28 and lines 22 and I5 to the azeotropic distillate in fractionating column 24 or the overhead may be passed via line |23 controlled by valve |30. condensed in condenser |3| and co1- lected in collecting tank |32. The condensate is witdrawn from the bottom of the collecting tank by pump |33 and part thereof may be passed via line |34 controlled by valve |35 to fractlonatlng column |25 to serve as reux for the fractionation. The remaining portion of the condensate is passed via line |36 controlled by valve |31 into storage tank I1.

. The extraction in extractor 86 with certain selective solvents such as, for example, tetra ethylene glycol, may extract some of the hydrocarbons together with the azeotrope former, such hydrocarbons being the relatively less paratlinic hydrocarbons such as the naphthenes. In such case. the bottoms from the extractor 85 may be passed via line |38 controlled by valve |39 into a separator or rejector |40 where the hydrocarbons contained in the mixture may be separated from the selective solvent and azeotrope former. This is accomplished by passing Water from tank IM through line |42 controlled by valve |53 and pumped by pump |44 through line |45 where it is mixed with the bottoms from the extractor 86 and passed into the separator |46. The water causes the mixture to separate into two phases. The upper phase of hydrocarbon oil may be recycled Via lines |45 and |61 controlled by valve |45 and through heater |04 into fractionating column |05 where any traces of azeotrope former may be removedin which case these hydrocarbons are commingled with the hydrocarbons from extractor 56 and passed into storage tank 91. If it is desired to recover the hydrocarbons of intermediate parainlcity, these may be passed to suitable storage via line |49 controlled by valve |50. The lower phase in the separator |49 consisting of the selective solvent, azeotrope former and water is withdrawn via line |5|, controlled by valve |52 and passed to the fractionating column |25 where the azeotrope former is separated from the selective solvent as described above. The selective solvent is withdrawn from the bot- .tom of the fractionating column |25 via line |53 controlled by valve |54 and is pumped by pump |55 through cooler |56 and line |51 to storage tank 88. When employing the hydrocarbon rejection with water in separator |40, it is preferable to provide the fractionating column |25 with a draw-off line |58 provided with valve |59 from which the water may be passed through cooler |50 and line |6| to water storage tank MI.

'As indicated above, the lower layer in separator 32 passing vthrough line 33 consisting of the greater portion of the Water and containing methyl ethyl ketone may also be passed into the fractionating column |25 for the recovery of the azeotrope former as described above.

It has been found in some cases, particularly when treating higher boiling hydrocarbon frac- The solution of selective solvent. water and tions, such as those boiling in the lubricating oil.

Diesel oil and spray oil range by azeotropic distillation, that the azeotropic distillate may be cooled under controlled conditions to separate first the *nore paraflinic oil -fractions and then the less parafflnic oil fractions from the azeotrope former. Thus, in the drawing, this is accomplished by controlling the temperature in condenser 28 so that theseparation in separator 32 permits the vseparation of an upper layer ofthe more paraflnic oil fractions, leaving the less paramnc oil fraction dissolved in the azeotrope former as a lower layer. By cooling the latter further and settling, the less parainic oil fraction may be stratied from the azeotrope former. If desired, the latter separation of the mixture of azeotrope former and relatively less parainnic oil fractions may be accomplishedv by passing the mixture into the separator U30 where it may be mixed with water from tank mi as described above.

The use of methyl ethyl ketone as an azeotrope former is specifically claimed in my prior abandoned application Serial No. 360,264, filed October 8, 1940.

The foregoing description of my invention is not to be taken as limiting my invention but only as illustrative thereof since many variations may be made by those skilled in the art without departing from the scope of the following claims.

I claim:

1. In a process for the treatment of a hydrocarbon fraction containing toluene and non-aromatic hydrocarbons to separate toluene from the non-aromatic hydrocarbons contained therein which ordinarily distill from said hydrocarbon fraction in the same temperature range as toluene distills therefrom which comprises azeotropically distilling said hydrocarbon fraction in the presence of a suihcient amount of methyl ethyl ketone to vaporize the non-aromatic hydrocarbons together with the methyl ethyl ketone thereby leaving toluene in the residue substantially completely separated from the hydrocarbons other` than toluene, the steps or" extracting by solution of the methyl ethyl ketone in said vaporized mixture in an extraction zone in countercurrent with an amount of tetra ethylene glycol suiiicient to dissolve said methyl ethyl ketone and separating a solution of said tetra." ethylene glycol and methyl ethyl ketone from said non-aromatic hydrocarbons.

2. In a process for the treatment of a complex hydrocarbon fraction to separate chemically similar hydrocarbon components therefrom from other hydrocarbon components contained therein. which ordinarily distill from the hydrocarbon fraction in the same temperature range as said chemically similar hydrocarbon components dis- A till therefrom which comprises azeotropically distilling said complex hydrocarbon fraction in the presence of a sufficient amount of methyl ethyl ketone to Vaporize at least one of the components contained therein together with the methyl ethyl ketone thereby leaving at least one of the components contained in said complex hydrocarbon fraction in the residue, the steps of extracting by solution of the methyl ethyl ketone in said vaporized mixture in an extraction zone in countercurrent with an amount of tetraethylene glycol sufficient to dissolve said methyl ethyl ketone and separating a solution of said tetraethylene vglycol and methyl ethyl ketone from said hydrocarbon component,

f GEORGE R. LAKE.

REFERENCES CITED The following references are of. record in the ille of this patent:

UNTTED STATES PATENTS Number Name Date 1,079,004 Golodetz Nov. 18, 1913 1,866,800 Deanesly July 12, 1932 2,085,546 Roelfsema June 29, 1937 2,212,810 Field Aug. 27, 1940 2,265,220 Sullivan Dec. 9, 1941 2,290,636 Deanesly July 21, 1942 2,333,856 Gerhold Nov. 9, 1943 2,360,655 Deanesly Oct. 17, 1944 2,370,063 Nutting et al Feb. 20, 1945 2,388,040 Clark Oct. 30, 1945 OTHER REFERENCES Perry Chemical Engineer Handbook, 2d edition, page 1214. 

